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Abstract:

A substrate processing apparatus is disclosed. The substrate processing
apparatus includes a process chamber configured to accommodate a
substrate; a gas supply unit configured to supply a process gas into the
process chamber; a lid member configured to block an end portion opening
of the process chamber; an end portion heating unit installed around a
side wall of an end portion of the process chamber; and a thermal
conductor installed on a surface of the lid member in an inner side of
the process chamber, and configured to be heated by the end portion
heating unit.

Claims:

1. A substrate processing apparatus comprising: a process chamber
configured to accommodate a substrate; a gas supply unit configured to
supply a process gas into the process chamber; a lid member configured to
block an end portion opening of the process chamber; an end portion
heating unit installed around a side wall of an end portion of the
process chamber; and a thermal conductor installed on a surface of the
lid member in an inner side of the process chamber, and configured to be
heated by the end portion heating unit.

2. The substrate processing apparatus of claim 1, further comprising: a
substrate holding unit configured to hold a plurality of substrates
accommodated in the process chamber; and a substrate heating unit
configured to heat the plurality of substrates held by the substrate
holding unit.

3. The substrate processing apparatus of claim 2, further comprising a
heat insulator installed between the substrate holding unit and the end
portion of the process chamber, wherein the end portion heating unit is
installed below a top portion of the heat insulator.

4. The substrate processing apparatus of claim 1, wherein the end portion
heating unit is a lamp heater.

5. The substrate processing apparatus of claim 4, wherein the lamp heater
is configured to directly heat the thermal conductor via the end portion
of the process chamber consists of a transparent member through which
light transmits.

6. The substrate processing apparatus of claim 1, further comprising a
control unit configured to control the end portion heating unit to heat
the thermal conductor while the process gas is being supplied from the
gas supply unit to the substrate.

7. The substrate processing apparatus of claim 6, wherein the control
unit is configured to control the end portion heating unit such that a
temperature of the end portion heating unit is maintained at a
liquefaction prevention temperature at which the process gas is not
liquefied.

8. The substrate processing apparatus of claim 7, wherein the
liquefaction prevention temperature is in a range from 50 degrees C. to
300 degrees C.

10. The substrate processing apparatus of claim 1, wherein thermal
conductivity of the thermal conductor is 5 Wm/mK or greater.

11. The substrate processing apparatus of claim 1, wherein the thermal
conductor has a porous structure.

12. The substrate processing apparatus of claim 1, wherein the process
gas is water vapor or a vaporized gas of hydrogen peroxide water.

13. A method of manufacturing a semiconductor device comprising:
providing a substrate processing apparatus that includes: a process
chamber configured to accommodate a substrate; a gas supply unit
configured to supply a process gas into the process chamber; a lid member
configured to block an end portion opening of the process chamber; an end
portion heating unit installed around a side wall of an end portion of
the process chamber; and a thermal conductor installed on a surface of
the cover in an inner side of the process chamber, and configured to be
heated by the end portion heating unit, heating the thermal conductor by
the end portion heating unit while the process gas is supplied to the
substrate.

14. The method of claim 13, wherein the act of heating the thermal
conductor by the end portion heating unit comprises controlling the end
portion heating unit such that the temperature of the end portion heating
unit is maintained at a liquefaction prevention temperature at which the
process gas is not liquefied.

15. A non-transitory computer-readable recording medium storing a program
that causes a computer to perform a process using a substrate processing
apparatus that includes: a process chamber configured to accommodate a
substrate; a gas supply unit configured to supply a process gas into the
process chamber; a lid member configured to block an end portion opening
of the process chamber; an end portion heating unit installed around a
side wall of an end portion of the process chamber; and a thermal
conductor installed on a surface of the cover in an inner side of the
process chamber, and configured to be heated by the end portion heating
unit, the process comprising heating the thermal conductor by the end
portion heating unit while the process gas is supplied to the substrate.

16. The non-transitory computer-readable recording medium of claim 15,
wherein the act of heating the thermal conductor by the end portion
heating unit includes controlling the end portion heating unit such that
the temperature of the end portion heating unit is maintained at a
liquefaction prevention temperature at which the process gas is not
liquefied.

Description:

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is based upon and claims the benefit of priority
from Japanese Patent Application No. 2012-168390, filed on Jul. 30, 2012,
the entire contents of which are incorporated herein by reference.

TECHNICAL FIELD

[0002] The present disclosure relates to a technique for processing a
substrate with a gas.

BACKGROUND

[0003] With decrease in size of large scale integrated circuits (LSIs),
processing techniques for controlling leakage current interference
between transistor elements are increasingly gaining technical
difficulties. LSI element isolation is achieved by a method of forming
gaps such as grooves or holes in a silicon (Si) substrate between
elements to be isolated, and depositing insulating material in the gaps.
The insulating material may often be an oxide film such as a silicon
oxide film. The silicon oxide film is formed by oxidation of the Si
substrate, CVD (Chemical Vapor Deposition), or SOD (Spin On Dielectric).

[0004] With recent miniaturization, to fill micro structures,
particularly, a gap structure, which is deep in a vertical direction or
narrow in a horizontal direction, with oxide, a filling method using a
CVD method has reached a technology limit. In response to this
background, a filling method using oxide having fluidity, i.e., SOD,
tends to be increasingly employed. For SOD, a coating insulating material
containing an inorganic or organic component called SOG (Spin On Glass)
is being used. Although this material has been employed for LSI
manufacturing processes before appearance of CVD oxide films, since
processing technology has non-fine feature size in a range from 0.35
μm to 1 μm or so, a modification method after coating was allowed
by performing heat treatment of 400 degrees C. in a nitrogen atmosphere.

[0005] On the other hand, there is an increasing need to reduce a thermal
load of transistors. The reason for reducing the thermal load includes
prevention of excessive diffusion of impurities, such as boron, arsenic,
phosphorus, and so on, which are injected for operation of transistors,
prevention of aggregation of metal silicide for electrodes, prevention of
performance variation of work function metal material for gates, secure
of writing/reading repetition lifetime of memory devices, etc.

[0006] However, since the minimum feature size of a semiconductor device
represented by recent LSI, DRAM (Dynamic Random Access Memory), or flash
memories is smaller than 50 μm width, it is difficult to achieve
miniaturization and improvement of manufacturing throughput while
maintaining quality, and make a process temperature low.

SUMMARY

[0007] The present disclosure provides some embodiments of a technique,
which are capable of improving manufacturing quality and throughput of
semiconductor devices.

[0008] According to one embodiment of the present disclosure, there is
provided a substrate processing apparatus including a process chamber
configured to accommodate a substrate; a gas supply unit configured to
supply a process gas into the process chamber; a lid member configured to
block an end portion opening of the process chamber; an end portion
heating unit installed around a side wall of an end portion of the
process chamber; and a thermal conductor installed on a surface of the
lid member in an inner side of the process chamber, and configured to be
heated by the end portion heating unit.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] FIG. 1 schematically illustrates a configuration of a substrate
processing apparatus according to a first embodiment.

[0010] FIG. 2 schematically illustrates a longitudinal sectional view of
the substrate processing apparatus according to the first embodiment.

[0011] FIG. 3 schematically illustrates a configuration of a controller of
the substrate processing apparatus which is appropriately used in the
first to third embodiments.

[0012] FIG. 4 schematically illustrates a configuration in the vicinity of
a furnace opening according to the first to third embodiments.

[0013] FIG. 5 schematically illustrates another configuration in the
vicinity of the furnace opening according to the first to third
embodiments.

[0014] FIG. 6A schematically illustrates another configuration in the
vicinity of the furnace opening according to the first to third
embodiments, and FIG. 6B schematically illustrates still another
configuration in the vicinity of the furnace opening according to the
first to third embodiments.

[0015] FIG. 7 schematically illustrates an example of positions of a gas
supply pipe and a gas exhaust pipe according to the first to third
embodiments.

[0016] FIG. 8 is a flow chart showing a substrate processing procedure
according to the first embodiment.

[0017] FIG. 9 is another flow chart showing a substrate processing
procedure according to the first embodiment.

[0018] FIG. 10 illustrates examples of film thickness obtained from
experiments conducted using the substrate processing apparatus according
to the first to third embodiments.

[0019] FIG. 11 schematically illustrates a substrate processing apparatus
according to the second embodiment.

[0020] FIG. 12 schematically illustrates a configuration of a hydrogen
peroxide vapor generator installed in the substrate processing apparatus
according to the second embodiment.

[0021] FIG. 13 is a flow chart showing a substrate processing procedure
according to the second embodiment.

[0022] FIG. 14 schematically illustrates a substrate processing apparatus
according to the third embodiment.

[0023] FIG. 15 schematically illustrates a longitudinal sectional view of
the substrate processing apparatus according to the third embodiment.

[0024] FIG. 16 is a flow chart showing a substrate processing procedure
according to the third embodiment.

DETAILED DESCRIPTION

First Embodiment

[0025] Hereinafter, a first embodiment is described.

(1) Configuration of Substrate Processing Apparatus

[0026] First, a configuration of a substrate processing apparatus
according to the present embodiment is described with reference to FIGS.
1 and 2. FIG. 1 schematically illustrates the configuration of the
substrate processing apparatus according to the present embodiment, in
which a portion of a processing furnace 202 is shown in a longitudinal
sectional view. FIG. 2 schematically illustrates a longitudinal sectional
view of the processing furnace 202 in the substrate processing apparatus
according to the present embodiment. For example, a procedure for
manufacturing a semiconductor device is performed in the substrate
processing apparatus.

(Processing Container)

[0027] As depicted in FIG. 1, the processing furnace 202 includes a
reaction tube 203 that serves as a processing container. The reaction
tube 203 is made of heat resistant material such as quartz (SiO2) or
silicon carbide (SiC), and has a cylindrical shape with its upper and
lower ends opened. A process chamber 201 is formed in a hollow
cylindrical portion of the reaction tube 203, and is configured to
accommodate a plurality of wafers 200 as substrates in such a state that
the wafers 200 are horizontally stacked in multiple stages along a
vertical direction by a boat 217 which will be described later.

[0028] A seal cap 219, which serves as a furnace port cover configured to
hermetically seal (or block) a lower end opening (i.e., furnace opening)
of the reaction tube 203, is installed under the reaction tube 203. The
seal cap 219 is configured to contact a lower end portion of the reaction
tube 203 from its bottom portion in a vertical direction. The seal cap
219 has a disc shape. The process chamber 201 serving as a substrate
processing space includes the reaction tube 203 and the seal cap 219.

(Substrate Support)

[0029] The boat 217, which is used as a substrate support, is configured
to support the plurality of wafers 200 in multiple stages. The boat 217
has a plurality of posts 217a for supporting the plurality of wafers 200.
In this embodiment, the number of the posts 217a is three. The plurality
of posts 217a is installed between a base plate 217b and a ceiling plate
217c. The plurality of wafers 200 is horizontally supported by the posts
217a in multiple stages along a tube-axial direction, with the centers of
the wafers 200 concentrically aligned. The ceiling plate 217c is formed
to be larger than a maximum outer diameter of the wafers 200 supported in
the boat 217.

[0030] The posts 217a, the base plate 217b, and the ceiling plate 217c are
made of nonmetallic material having high thermal conductivity, such as
silicon carbide (SiC), aluminum oxide (AlO), aluminum nitride (AlN),
silicon nitride (SiN), or zirconium oxide (ZrO). In particular,
nonmetallic material having thermal conductivity of 10 W/mK or greater
may be preferable. If the thermal conductivity is not a concern, the
nonmetallic material may be quartz (SiO) or the like. If contamination of
the wafers 200 by metal is not problematic, the posts 217a and the
ceiling plate 217c may be made of metal material such as stainless steel.
If the posts 217a and the ceiling plate 217c are made of metal, a film of
ceramics or Teflon® may be coated on the metal.

[0031] A heat insulator 218 made of heat resistant material such as quartz
or silicon carbide is installed under the boat 217 and is configured to
prevent heat from being transferred from a first heating part 207 to the
seal cap 219. The heat insulator 218 functions not only as a heat
insulating member, but also as a holder for holding the boat 217. In
addition, the heat insulator 218 is not limited to a plurality of
disc-like heat insulating plates, which are horizontally stacked in
multiple stages, as shown, but may be a cylindrical quartz cap or the
like. The heat insulator 218 may be also considered as one of components
of the boat 217.

(Elevating Unit)

[0032] A boat elevator as an elevating unit for elevating the boat 217 to
transfer into or out of the reaction tube 203 is installed below the
reaction tube 203. The seal cap 219 for sealing the furnace opening when
the boat 217 is ascended by the boat elevator is installed in the boat
elevator.

[0033] A boat rotation mechanism 267 for rotating the boat 217 is
installed at a side of the seal cap 219 opposite to the process chamber
201. A rotary shaft 261 of the boat rotation mechanism 267 is connected
to the boat 217 via the seal cap 219 and is configured to rotate the
wafers by rotating the boat 217.

(First Heating Part)

[0034] The first heating part 207 for heating the wafers 200 in the
reaction tube 203 is installed outside the reaction tube 203 and has a
concentric shape to surround a side wall of the reaction tube 203. The
first heating part 207 is supported by a heater base 206. As illustrated
in FIG. 2, the first heating part 207 includes first to fourth heater
units 207a to 207d. The first to fourth heater units 207a to 207d are
installed along a stacked direction of the wafers 200 in the reaction
tube 203.

[0035] As temperature detectors for detecting a temperature of the wafers
200 or an ambient temperature, first to fourth temperature sensors 263a
to 263d such as thermocouples are installed, respectively, to the first
to fourth heater units 207a to 207d, between the reaction tube 203 and
the boat 217. Also, sets of wafers 200 in the plurality of wafers 200 are
heated by the heater units 207a to 207d, respectively, and the first to
fourth temperature sensors 263a to 263d may be installed to detect
temperatures of wafers 200, respectively, which are located in the middle
of the sets of wafers 200.

[0036] A controller 121, which will be described later, is electrically
connected to the first heating part 207 and the first to fourth
temperature sensors 263a to 263d. To control the temperature of the
wafers 200 in the reaction tube 203 to be a predetermined temperature,
the controller 121 is configured to perform individually setting and
adjusting a temperature of each of the first to fourth heater units 207a
to 207d, by controlling the supply of electric power to the first to
fourth heater units 207a to 207d at predetermined timings, based on
temperature information that is detected by the first to fourth
temperature sensors 263a to 263d.

(Gas Supply Unit)

[0037] As illustrated in FIG. 1, a gas supply pipe 233 serving as a gas
supply unit for supplying a vaporized precursor as a process gas into the
reaction tube 203 is installed outside the reaction tube 203. The
vaporized precursor may have a boiling point in a range from 50 degrees
C. to 200 degrees C. In this embodiment, the vaporized precursor may be
water vapor (H2O).

[0038] The gas supply pipe 233 is connected to a gas supply nozzle 401
that is installed in the reaction tube 203. The gas supply nozzle 401 is
installed along the stacked direction of the wafers 200 from a bottom
portion to a top portion of the reaction tube 203. The gas supply nozzle
401 is formed to have a plurality of gas supply holes 402 through which
the water vapor can evenly be supplied into the reaction tube 203. The
gas supply pipe 233 is connected to a water vapor generator 260. Water
vapor generated in the water vapor generator 260 rises from the bottom
portion of the reaction tube 203 into the gas supply nozzle 401, and is
supplied into the reaction tube 203 through the plurality of gas supply
holes 402.

[0039] The water vapor generator 260 is connected with a hydrogen gas
supply pipe 232a and an oxygen gas supply pipe 232b. A hydrogen gas
supply source 240a, a mass flow controller (i.e., MFC or a flow rate
controller) 241a, and an opening/closing valve 242a are sequentially
installed in the hydrogen gas supply pipe 232a from an upstream side. An
oxygen gas supply source 240b, an MFC 241b, and an opening/closing valve
242b are sequentially installed in the oxygen gas supply pipe 232b from
an upstream side. The water vapor generator 260 generates the water vapor
by using hydrogen gas supplied from the hydrogen gas supply source 240a
and oxygen gas supplied from the oxygen gas supply source 240b.

[0040] An inert gas supply pipe 232c is connected to a portion of the gas
supply pipe 233. An inert gas supply source 240c, an MFC 241c, and an
opening/closing valve 242c are sequentially installed in the inert gas
supply pipe 232c from an upstream side. A gas flow rate control unit 283
is electrically connected to the MFCs 241a, 241b, and 241c and the valves
242a, 242b, and 242c and is configured to control flow rates of the
supplied gases at desired timings such that the flow rates reach desired
values.

[0042] One end of a gas exhaust pipe 231 for exhausting gas in the process
chamber 201 is connected to a lower portion of the reaction tube 203. The
other end of the gas exhaust pipe 231 is connected to a vacuum pump 246a
(i.e., exhauster) via an auto pressure controller (APC) valve 255. An
interior of the process chamber 201 is exhausted by a negative pressure
generated in the vacuum pump 246a. The APC valve 255 is an
opening/closing valve capable of performing or stopping exhaust of the
process chamber 201 by opening or closing the valve. This valve also
serves as a pressure adjusting valve that is capable of adjusting a
pressure by adjusting a degree of opening the valve. A pressure sensor
223 serving as a pressure detector is installed at an upstream side of
the APC valve 255. In this manner, the exhaust unit is configured to
vacuum-exhaust the interior of the process chamber 201 such that an
internal pressure of the process chamber 201 reaches a predetermined
pressure (i.e., degree of vacuum). A pressure control unit is
electrically connected to the process chamber 201 and the pressure sensor
223 by the APC valve 255 and is configured to control the internal
pressure of the process chamber 201 based on a pressure detected by the
pressure sensor 223 such that the internal pressure reaches a desired
pressure by using the APC valve 255.

[0043] The exhaust unit includes the gas exhaust pipe 231, the APC valve
255, the pressure sensor 223, etc. The exhaust unit may further include
the vacuum pump 246.

(Second Heating Part)

[0044] In the course of research and development, the inventors of the
present disclosure have found a problem that couldn't happen in
conventional processes in a range from about 300 degrees C. to 400
degrees C., or higher. The problem was that in the process in a range
from room temperature to 300 degrees C. or so, a vaporization precursor
as a process gas in the reaction tube 203 is cooled to a temperature
lower than a boiling point of the vaporization precursor, and thus, is
liquefied. It has proved through research that such liquefaction is
caused much in a lower portion of the boat 217 and around the heat
insulator 218 and the gas exhaust pipe 231. It has also been found that
this liquefaction occurs below the heat insulator 218 and at positions
apart from the wafers 200.

[0045] In addition, the inventors have found problems that alien
substances are produced on the wafers 200, and when the plurality of
wafers 200 is processed, film thickness differences occur among the
respective wafers 200.

[0046] Accordingly, the inventors of the present disclosure have tried to
resolve the above problems by installing a liquefaction prevention heater
280 as a second heating part (i.e., thermal conductor heating part) as
shown in FIGS. 1 and 2.

[0047] Herein, the term "liquefaction" is intended to include phenomena
such as dew condensation and coagulation.

[0048] FIG. 4 illustrates a sectional view of the seal cap 219 and the
lower portion (i.e., furnace opening portion) of the reaction tube 203.
As depicted in FIG. 4, the liquefaction prevention heater 280 serving as
the second heating part is installed in the lower portion of the reaction
tube 203, above the seal cap 219 and around a side wall of the reaction
tube 203. The second heating part may be installed below the first
heating part. The liquefaction prevention heater 280 may be configured
with a resistive heater 281 as shown in FIG. 4 or a lamp heater 282,
which is a radiative heating part, as shown in FIG. 5. A seal cap
protection part 272 for protecting the seal cap 219 from a vaporized
precursor is installed on the seal cap 219. The seal cap protection part
is made of material which is difficult to react with the vaporized
precursor, for example, nonmetallic material such as quartz (SiO2)
or the like. An O-ring (i.e., seal member) for maintaining airtightness
is installed at the lower end portion of the reaction tube 203, between
the seal cap protection part 272 and the seal cap 219. An O-ring
protection part 273 having a cooling passage 274 is installed in the
lower end portion of the reaction tube 203. Also, a cooling passage 270
is installed in the seal cap 219. The cooling passages 274 and 270 can
prevent the O-ring from being deteriorated and the seal cap 219 from
being deformed because of heat emitted from the liquefaction prevention
heater 280 and emitted from the first to fourth heater units 207a to
207d. In the case where the seal cap and the seal cap protection part 272
are cooled, and thus, dew condensation occurs on surfaces of the seal cap
and the seal cap protection part 272, a heat conduction part (i.e.,
thermal conductor) 271 may be installed on the seal cap protection part
272 to allow the surface of the seal cap protection part 272 to be easily
heated, as illustrated in FIGS. 4 and 5. The heat conduction part 271 is
made of the same kind of the material as the boat 217, for example,
nonmetallic material having high thermal conductivity, such as silicon
carbide (SiC), aluminum oxide (AlO), aluminum nitride (AlN), boron
nitride (BN), silicon nitride (SiN), or zirconium oxide (ZrO), or carbon
material such as graphite or glassy carbon. The thermal conductivity may
be 5 Wm/mK or greater. Since it is likely that the heat conduction part
is in contact with the precursor gas, the heat conduction part may be
made of material which does not react with the precursor gas. In
addition, the heat conduction part 271 may be configured to have a
self-heating function by including a conductive member and flowing
electric current into the conductive member. Additionally, the heat
conduction part 271 may be formed to have a porous structure to increase
an evaporation area. The lamp heater 282 may be configured to directly
heat the seal cap protection part 272 and the heat conduction part 271
via a transparent member through which light transmits. In this case, the
transparent member corresponds to a portion of the reaction tube 203,
which is made of, for example, quartz. If it is not intended that the
wafers 200 are heated by the lamp heater 282, an opaque member may be
used instead of the transparent member or an awning may be further
installed. Further, the seal cap protection part 272 may be made of SiC
and the heat conduction part 271 may be made of quartz. The above
configuration can prevent contamination while the furnace opening portion
is heated.

(One Type of Liquefaction Prevention Heater)

[0049] One type of the liquefaction prevention heater 280 is illustrated
in FIG. 6A. As shown in FIG. 6A, the lamp heater 282 is installed in the
liquefaction prevention heater 280 to surround an entire circumference of
the reaction tube 203. A heat insulating member 286 is installed around
the lamp heater 282. As the lamp heater 282 is installed to surround the
entire circumference of the reaction tube 203, an entire lower portion of
the reaction tube 203 can be evenly heated. In addition, the heat
insulating member 286 can contribute to improving thermal efficiency of
the lamp heater 282, which may decrease power consumption, while reducing
thermal effect on other devices and controllers which are out of the
reaction tube 203. An example of the heat insulating member 286 may
include alumina cloth or the like.

(Another Type of Liquefaction Prevention Heater)

[0050] Another type of liquefaction prevention heater 280 is illustrated
in FIG. 6B. As shown in FIG. 6B, a plurality of separate lamp heaters
283a, 283b, 283c, 283d, 283e, and 283f is installed in the liquefaction
prevention heater 280. By providing the plurality of separate lamp
heaters as depicted in FIG. 6B, it is possible to adjust an amount of
heat that is supplied to portions that are easy to be heated, and
portions that are hard to be heated. This allows desired places to be
heated evenly. For example, if the entire circumference is heated with
the lamp heater 282, since a shadow is formed in the heat insulator 218
by the posts 217a of the boat 217, it is difficult to heat the entire
circumference evenly. If the separated lamp heaters 283a to 283f are
installed at positions which do not face the posts 217a, since no shadow
is formed in the heat insulator 218, it is possible to heat the entire
circumference evenly.

(Lamp Heater)

[0051] The inventors of the present disclosure have also conducted
intensive research and development for how to increase heating efficiency
of a vaporized precursor by the lamp heater 282 and it has been
consequently proved that the heating efficiency can be improved by
adjusting a wavelength of light emitted from the lamp heater 282.

[0052] For example, if the vaporized precursor is hydrogen peroxide water
or water containing water molecules (H2O), a lamp capable of
emitting light having a wavelength which can be easily absorbed by the
water molecules may be used to improve the heating efficiency. The light
having the wavelength which can be easily absorbed by the water molecules
corresponds to infrared rays having a wavelength in a range from about
0.7 μm to about 250 μm. Any lamp capable of emitting the infrared
rays in the above wavelength band may be used to improve the heating
efficiency. Specifically, the lamp may emit light in a range from about
1.3 μm to about 200 μm. More specifically, the lamp may emit light
in a range from about 2 μm to about 20 μm. Still more specifically,
the lamp may emit light in a range from about 2 μm to about 4.5 μm,
which corresponds to a medium infrared ray. Examples of the lamp may
include a Cantal wire heater with an emission peak wavelength of about
2.2 μm. Additionally, a carbon heater, a SiC heater, a tungsten lamp,
a halogen lamp, and the like may be used.

(Position of Liquefaction Prevention Heater)

[0053] The liquefaction prevention heater 280 may be installed below a
lower end portion of the heat insulator 218, as shown in FIG. 1. The
lower portion of the reaction tube 203, a connection portion of the
reaction tube 203 and the gas exhaust pipe 231, and a connection portion
of the reaction tube 203 and the gas supply pipe 233 are heat-insulated
from the first heating part 207 by the heat insulator 218 to be
maintained in a low temperature state. Therefore, surrounding
environments of the lower portion of the reaction tube 203, the
connection portion of the reaction tube 203 and the gas exhaust pipe 231,
and the connection portion of the reaction tube 203 and the gas supply
pipe 233 have an atmosphere where a process gas supplied into the
reaction tube 203 may be liquefied. This liquefaction can be prevented by
the liquefaction prevention heater 280 installed below an upper end
portion of the heat insulator 218.

(Exhaust Heating Part)

[0054] As depicted in FIGS. 6A, 6B, and 7, an exhaust tube heater 284
serving as an exhaust heating part for heating the gas exhaust pipe is
installed to the gas exhaust pipe 231. The exhaust tube heater 284 is
controlled to a desired temperature, e.g., in a range from 50 degrees C.
to 300 degrees C., to prevent dew condensation in the gas exhaust pipe
231.

(Supply Heating Part)

[0055] As depicted in FIGS. 6A, 6B, and 7, an inlet tube heater 285
serving as a supply heating part is installed between the gas supply pipe
233 and the reaction tube 203. The inlet tube heater 285 is controlled to
a desired temperature, e.g., in a range from 50 degrees C. to 300 degrees
C., to prevent dew condensation in the gas supply pipe 233.

(Liquefaction Prevention Control Part)

[0056] As depicted in FIGS. 6A and 6B, a liquefaction prevention
controller 287 serving as a liquefaction prevention control part for
controlling a temperature of the lamp heater 282, the exhaust tube heater
284, and the inlet tube heater 285 to a liquefaction prevention
temperature is installed.

[0057] A temperature detector 288 for detecting the temperature of the
lamp heater 282, the exhaust tube heater 284, and the inlet tube heater
285 is installed in the liquefaction prevention controller 287. An
example of the temperature detector 288 may include a sheath type
thermocouple. Amounts of electric power supplied to the lamp heater 282,
the exhaust tube heater 284, and the inlet tube heater 285 are controlled
based on the temperature detected by the temperature detector 288. For
example, the electric power is controlled to enter an ON state when the
temperature of the lamp heater 282, the exhaust tube heater 284, and the
inlet tube heater 285 reaches 100 degrees C or less, and an OFF state
when the temperature reaches 300 degrees C. or more. Instead of the above
ON/OFF control, feedback control such as proportional integral
differential (PID) control may be performed to hold the heaters 282, 284,
and 285 at a desired temperature (e.g., 200 degrees C.). The lamp heater
282 may perform the ON/OFF control at least during the supply of the
process gas and may be put in the OFF state when the wafers 200 are not
present in the process chamber 201 or when the wafers 200 are subjected
to treatment of 300 degrees C. or more.

[0058] Although FIGS. 1 and 2 illustrate that the gas supply pipe 233 and
the gas exhaust pipe 231 are installed at opposite positions, the pipes
may be installed at the same side, as illustrated in FIGS. 6A, 6B, and 7.
Since empty spaces in a substrate processing apparatus or empty spaces in
a semiconductor device manufacturing plant equipped with a plurality of
substrate processing apparatuses are narrow, it is possible to easily
perform maintenance of the gas supply pipe 233, the gas exhaust pipe 231,
and the liquefaction prevention heater 280 by installing the gas supply
pipe 233 and the gas exhaust pipe 231 at the same side as described
above.

(Control Part)

[0059] As illustrated in FIG. 3, a controller 121, which is a control unit
(or a control part), may be configured as a computer including a central
processing unit (CPU) 121a, a random access memory (RAM) 121b, a memory
device 121c, and an I/O port 121d. The RAM 121b, the memory device 121c,
and the I/O port 121d are configured to exchange data with the CPU 121a
via an internal bus 121e. An input/output device 122, for example,
including a touch panel or the like, is connected to the controller 121.

[0060] The memory device 121c is configured with, for example, a flash
memory, a hard disc drive (HDD), or the like. A control program for
controlling operations of the substrate processing apparatus or a process
recipe, in which a sequence or condition for processing a substrate
described later is written, is readably stored in the memory device 121c.
Also, the process recipe functions as a program for the controller 121 to
execute each sequence in the substrate processing process, which will be
described later, to obtain a predetermined result. Hereinafter, such a
process recipe or control program may be generally referred to as "a
program." Also, when the term "program" is used herein, it may indicate a
case of including only a process recipe, a case of including only a
control program, or a case of including both a process recipe and a
control program. In addition, the RAM 121b is configured as a memory area
(or a work area) in which a program or data read by the CPU 121a is
temporarily stored.

[0062] The CPU 121a is configured to read and execute the control program
from the memory device 121c. The CPU 121a also reads the process recipe
from the memory device 121c according to an input of an operation command
from the input/output device 122. In addition, the CPU 121a is configured
to control the flow rate adjusting operation of liquid precursor by the
liquid mass flow controller 294, the flow rate adjusting operation of
various gases by the MFCs 241a, 241b, 241c, 241d, 299b, 299c, 299d, and
299e, the opening and closing operation by the valves 242a, 242b, 242c,
242d, 234, 240, 295a, 295b, 295c, 295d, and 295e, the shuttering
operation by the shutters 252, 254, and 256, the opening and closing
adjusting operation by the APC valve 255, the temperature adjusting
operation of the first heating part 207 based on the first to fourth
temperature sensors 263a to 263d, the temperature adjusting operation of
the third heating part 209 based on the temperature sensors, the starting
and stopping of the vacuum pumps 246a and 246b, the rotation speed
regulating operation of the blower rotation mechanism 259, the rotation
speed regulating operation of the boat rotation mechanism 267, the
temperature control of the liquefaction prevention heater 280 (i.e.,
second heating part) by the liquefaction prevention controller 287, a
hydrogen peroxide vapor generator 307 by the temperature controller 400,
and the like, according to contents of the read process recipe.

[0063] Moreover, the controller 121 is not limited to being configured as
a dedicated computer but may be configured as a general-purpose computer.
For example, the controller 121 according to one embodiment may be
configured by preparing an external memory device 123 (for example, a
magnetic tape, a magnetic disc such as a flexible disc or a hard disc, an
optical disc such as a CD or DVD, a magneto-optical disc such as an MO, a
semiconductor memory such as a USB memory or a memory card), in which the
program is stored, and installing the program on the general-purpose
computer using the external memory device 123. Also, means for supplying
a program to a computer is not limited to the case in which the program
is supplied through the external memory device 123. For example, the
program may be supplied using communication means such as the Internet or
a dedicated line, rather than through the external memory device 123.
Also, the memory device 121c or the external memory device 123 is
configured as a non-transitory computer-readable recording medium.
Hereinafter, the means for supplying the program will be simply referred
to as "a recording medium." In addition, when the term "recording medium"
is used herein, it may include a case of including only the memory device
121c, a case of including only the external memory device 123, or a case
of including both the memory device 121c and the external memory device
123.

(2) Substrate Processing Procedure

[0064] Hereinafter, a substrate processing procedure performed as one of
procedures for manufacturing a semiconductor device according to the
present embodiment is described with reference to FIG. 8. This procedure
is performed by the above-described substrate processing apparatus. In
the present embodiment, as an example of such a substrate processing
procedure, a procedure (e.g., modification processing procedure) of using
a vaporized gas, which is obtained by vaporizing hydrogen peroxide, as a
process gas to modify (or oxidize) a silicon (Si)-containing film, which
is formed on a wafer 200 as a substrate, into a silicon oxide film is
described. In the following descriptions, the operation of various
components of the substrate processing apparatus is controlled by the
controller 121 illustrated in FIGS. 1 and 3.

[0065] Here, an example of using a substrate having an uneven structure,
which is a micro structure, as a wafer 200, where at least a concave
portion (i.e., groove) is filled with polysilazane (SiH2NH) to form
a silicon (Si)-containing film in the groove, and using a vaporized gas
of hydrogen peroxide water as a process gas is described. The
silicon-containing film contains silicon (Si), nitrogen (N), and hydrogen
(H) and, in some cases, may further contain carbon (C) and other
impurities. A substrate having a micro structure refers to a substrate
having a structure with a high aspect ratio, such as a deep groove (i.e.,
concave portion) in the direction perpendicular to the substrate or a
laterally narrow groove (i.e., concave portion) having a width from 10 nm
to 50 nm.

[0066] Polysilazane is a substitute material for SOG which has been
conventionally used. For example, polysilazane is obtained by catalytic
reaction of ammonia with dichlorosilane or trichlorosilane, and is used
to cover a substrate by using a spin coater so as to form a thin film. A
thickness of the film is regulated depending on the molecular weight and
viscosity of polysilazane and a rotation speed of the coater. A silicon
oxide film can be formed by supplying water to the polysilazane.

(Substrate Load Step (S10))

[0067] Initially, a predetermined number of the wafers 200 is loaded onto
the boat 217 (i.e., wafer charge). The boat 217 supporting the wafers 200
is lifted up by the boat elevator and is loaded into the reaction tube
203 (or the process chamber 201) (i.e., boat load). In this state, the
seal cap 219 seals the furnace opening of the processing furnace 202.

(Pressure and Temperature Adjustment Step (S20))

[0068] An interior of the reaction tube 203 is vacuum-exhausted by at
least one of the vacuum pumps 246a and 246b such that the internal
pressure of the reaction tube 203 reaches a desired pressure (e.g., from
96,000 Pa to 102,500 Pa, specifically, about 100,000 Pa). In this
operation, the internal pressure of the reaction tube 203 is measured by
the pressure sensor 223 and a degree of opening of the APC valve 242 and
opening or closing of the valve 240 is feedback-controlled based on the
measured pressure (i.e., pressure adjustment).

[0069] The wafers 200 accommodated in the reaction tube 203 are heated by
the first heating part 207 such that the temperature of the wafers 200
reaches a desired temperature (e.g., 40 degrees C. to 300 degrees C.,
specifically, about 150 degrees C.). In this operation, the supply of
electric power to the first to fourth heater units 207a to 207d in the
first heating part 207 is feedback-controlled based on temperature
information detected by the first to fourth temperature sensors 263a to
263d such that the temperature of the wafers 200 in the reaction tube 203
reaches the desired temperature (i.e., temperature adjustment). Here, the
first to fourth heater units 207a to 207d are controlled to have the same
set temperature.

[0070] While the wafers 200 are heated, the boat rotation mechanism 267 is
actuated to rotate the boat 217. A rotation speed of the boat 217 is
controlled by the controller 121. The boat 217 is maintained to be
rotated until at least the modification step (S30), which will be
described later, ends.

[0071] Electric power is also supplied to the lamp heater 282, the inlet
tube heater 285, and the exhaust tube heater 284 to adjust a temperature
of the heaters to be in a range from 100 degrees C. to 300 degrees C.
Specifically, the temperature of each of the lamp heater 282, the inlet
tube heater 285, and the exhaust tube heater 284 may be adjusted to about
200 degrees C. The three heaters may be controlled to have different
temperatures.

(Modification Step (S30))

[0072] When the wafers 200 are heated to reach the desired temperature and
the boat 217 reaches the desired rotation speed, water vapor is generated
by the water vapor generator 260 and is supplied into the process chamber
201. Nitrogen gas as an inert gas is also supplied from the inert gas
supply source 240c into the process chamber 201. Thus, the internal
pressure of the process chamber 201 is set to be in a range from 6,000 Pa
to 60,000 Pa and the water vapor partial pressure in the process chamber
201 is set to be in a range from 600 Pa to 6,000 Pa (i.e., water
concentration is set to be from 10% to 100%). Under the above conditions
of the temperature and the pressure, the wafers 200 are subjected to heat
treatment for 5 minutes to 120 minutes. Specifically, for example, under
the conditions in which the internal temperature of the process chamber
201 is about 200 degrees C., the internal pressure of the process chamber
201 is 53,200 Pa, and a vapor partial pressure in the process chamber is
45,800 Pa (i.e., water concentration is 86%), the wafers 200 are
subjected to heat treatment for 30 minutes. Due to the heat treatment
under the water vapor atmosphere and the reduced-pressure as described
above, a silicon-containing material coated on each of the wafers 200 is
oxidized.

[0073] After a predetermined period of time elapses, the valves 242a and
242b are closed and the supply of the water vapor into the reaction tube
203 is stopped.

(Purge Step (S40))

[0074] After the modification step (S30) ends, the APC valve 255 is opened
to vacuum-exhaust the interior of the reaction tube 203 so that remaining
water vapor is discharged out of the reaction tube 203. Specifically, as
the valves 242a and 242b are closed and the APC valve 255 is opened,
N2 gas (i.e., inert gas) as a purge gas is supplied from the inert
gas supply pipe 232c into the reaction tube 203 via the gas supply nozzle
401 while a flow rate of the purge gas is controlled by the mass flow
controller 241c, so as to exhaust the interior of the process chamber
201. Examples of the purge gas may include a rare gas such as He gas, Ne
gas, Ar gas, and the like, in addition to the inert gas such as nitrogen
(N2) gas. As such, it is possible to facilitate purging of the
remaining gas to be discharged out of the reaction tube 203.

(Temperature Decrease and Return-to-Atmospheric Pressure Step (S50))

[0075] After the purge step (S40) ends, the APC valve 255 or the vacuum
pump 246a is adjusted to return the internal pressure of the reaction
tube 203 to atmospheric pressure while the temperature of the wafers 200
is decreased to a predetermined temperature (e.g., room temperature or
so). Specifically, while the valve 242c is opened, N2 gas as an
inert gas is supplied into the reaction tube 203 to increase the internal
pressure of the reaction tube 203 to atmospheric pressure. Electric power
supplied to the first heating part 207 and the liquefaction prevention
heater 280 (i.e., second heating part) is controlled to decrease the
temperature of the wafers 200.

[0076] When the temperature of the wafers 200 is decreased, the shutters
252, 254, and 256 may be opened, with a blower 257 actuated, to supply a
cooling gas from a cooling gas supply pipe 249 into a space 262 between
the reaction tube 203 and a heat insulating member 210 and exhaust the
cooling gas via a cooling gas exhaust pipe 253, while a flow rate of the
cooling gas is controlled by a mass flow controller 251. Examples of the
cooling gas may include a rare gas (such as He gas, Ne gas, and Ar gas),
air, or the like, alone or in combination, in addition to N2 gas.
Thus, the space 262 can be rapidly cooled so that the reaction tube 203
and the first heating part 207 installed in the space 262 can be cooled
in a short time. In addition, the temperature of the wafers 200 in the
reaction tube 203 can be decreased in a shorter time.

[0077] In addition, the cooling gas such as N2 gas is supplied from
the cooling gas supply pipe 249 into the space 262 such that the space
262 is filled and cooled with the cooling gas while the shutters 254 and
256 are closed, and the shutters 254 and 256 may then be opened, with the
blower 257 actuated, to exhaust the cooling gas in the space 262 via the
cooling gas exhaust pipe 253.

(Substrate Unload Step (S60))

[0078] The seal cap 219 is then descended by the boat elevator to open the
bottom portion of the reaction tube 203 and, with the processed wafers
200 held on the boat 217, the wafers 200 are unloaded from the bottom
portion of the reaction tube 203 out of the reaction tube 203 (or the
process chamber 201) (i.e., boat unload). Subsequently, the processed
wafers 200 are taken out of the boat 217 (i.e., wafer discharge) and the
substrate processing procedure according to the present embodiment ends.

[0079] Although the water vapor herein is illustrated and described as
being simply supplied to the silicon-containing film at a low
temperature, the wafers 200 may be annealed subsequent to the
modification step (S30), as illustrated in FIG. 9. The case of performing
an annealing step (S80) is described below.

(Pressure and Temperature Adjustment Step (S70))

[0080] After the modification step (S30) ends, the internal temperature of
the process chamber 201 is increased to be in a range from 600 degrees C.
to 1,100 degrees C. In addition, water vapor is supplied from the water
vapor generator 260 into the process chamber 201 and nitrogen gas as an
inert gas is supplied from the inert gas supply source 240c into the
process chamber 201. Thus, the internal pressure of the process chamber
201 is set to be in a range from 6,000 to 60,000 Pa and the water vapor
partial pressure is set to be in a range from 600 to 60,000 Pa (i.e.,
water concentration is set to be from 10% to 100%). Specifically, in the
present embodiment, the internal temperature of the process chamber 201
may be increased from the temperature in the modification step to 800
degrees C. for 120 minutes. In addition, since the temperature has
started to increase in the pressure and temperature adjustment step
(S70), the lamp heater 282, the inlet tube heater 285, and the exhaust
tube heater 284 are turned off. In this operation, the heaters may be
turned off at either the same timing or different timings. For example,
because gas is flown into the gas supply pipe 233 and the gas exhaust
pipe 231 during the annealing step, only the lamp heater 282 may be
turned off, while the other heaters are turned on.

(Annealing Step (S80))

[0081] The wafers 200 are subjected to annealing for 5 minutes to 120
minutes under the above conditions of the temperature and the pressure.
Specifically, in this embodiment, the wafers 200 may be subjected to
annealing for 30 minutes under the conditions in which the temperature is
about 800 degrees C., the pressure is 53,200 Pa, and the water vapor
partial pressure is 45,800 Pa (i.e., water concentration is 86%).

(Purge Step (S40))

[0082] After the annealing step (S40) ends, the purge step S40 as
described above is performed.

(Temperature Decrease and Return-to-Atmospheric Pressure Step (S100))

[0083] After the purge step ends, the temperature is decreased to reach a
temperature at which the wafers can be extracted.

(Substrate Unload Step (S60))

[0084] The wafers 200 are unloaded from the process chamber 201 according
to the substrate unload step as described above.

[0085] The substrate processing procedure according to the present
embodiment has been described above. A cleaning step may be actually
performed subsequent to the substrate unload step (S60) in the substrate
processing procedure. This cleaning step can remove impurities remaining
in the reaction tube 203, the boat 217, the inlet tube, and the exhaust
tube, so as to prevent corrosion of members installed in the reaction
tube 203.

(3) Effects of the First Embodiment

[0086] The first embodiment can achieve one or more effects as described
below.

[0087] (a) According to the first embodiment, it is possible to prevent
the vaporized precursor from being liquefied in the lower portion of the
reaction tube 203.

[0088] (b) Also, it is possible to reduce an amount of alien substances
attached to the substrates. In some cases where the vaporized precursor
is liquefied, such liquid may absorb alien substances existing on
surfaces of members in the process chamber 201 and may be again vaporized
and attached to the wafers 200, resulting in generating different alien
substances. According to the present embodiment, since the vaporized
precursor can be prevented from being liquefied, the amount of alien
substances attached to the substrates can be reduced.

[0089] (c) Additionally, it is possible to improve overall processing
uniformity in the process chamber 201. Specifically, when a plurality of
substrates is processed, difference in film thickness between the
substrates can be reduced.

[0090] FIG. 10 illustrates a relationship between difference in film
thickness of substrates and electric power outputted to the lamp heater
282. As illustrated in FIG. 10, given that a film thickness difference
when the lamp heater 282 is turned off is 100, when 20% and 40% of the
output power are applied, it is indicated that the film thickness
difference is reduced and overall processing uniformity in the process
chamber 201 is improved.

[0091] (d) Further, nitrogen and hydrogen in polysilazane are substituted
with oxygen by water molecules, so as to form a Si--O bonding.

[0092] (e) Furthermore, a silicon oxide film having a Si--O bonding, which
does not contain much of NH-- group, as a main skeleton can be formed as
the silicon-containing film. Also, this silicon oxide film has heat
resistance higher than that of a silicon oxide film made of conventional
organic SOG.

[0093] (f) In addition, according to the low temperature processing, a
groove in the micro structure can be uniformly processed, as compared to
high temperature processing. With the high temperature processing, a top
portion of the groove is first modified and a bottom portion of the
groove may not be modified. However, the low temperature processing can
prevent the top portion of the groove from being first modified when the
processing starts, which allows the groove to be uniformly processed.

[0094] (g) In addition, the annealing process can remove impurities, such
as nitrogen, hydrogen, and other impurities, in the silicon-containing
film existing in the deepest portion in the groove on the wafers 200. As
a result, the silicon-containing film can be sufficiently oxidized,
densified, and cured, thereby achieving an insulating film having a good
WER (Wafer Etching Rate) characteristic. WER has great dependency on
final anneal temperature. That is, a higher anneal temperature provides a
better WER characteristic.

[0095] (h) In addition, the annealing process can remove carbon (C) and
impurities contained in the silicon-containing film. The
silicon-containing film is typically formed by using a coating method
such as a spin coating method or the like. The spin coating method uses
liquid obtained by adding an organic solvent to polysilazane. However,
carbon and other impurities (e.g., elements other than Si and O) derived
from this organic solvent remain in the liquid.

[0096] (i) In addition, since the gas supply pipe 233 and the gas exhaust
pipe 231 are installed in the same side, maintenance can be easily
performed.

[0097] (j) Since a lamp emitting infrared rays is used for the lamp
heater, water molecules can be efficiently heated. A wavelength of the
infrared rays may be in a range, specifically, from about 0.7 μm to
about 250 μm, more specifically, from about 1.3 μm to about 200
μm, still more specifically, from about 2 μm to about 20 μm,
particularly specifically, from about 2 μm to about 4.5 μm.

[0098] (k) In addition, since the lamp heater can heat gas near the
furnace opening, an inner wall surface of the furnace opening, an inner
wall surface of the seal cap, and the like under a state where the seal
of the furnace opening is cooled, it is possible to prevent dew
condensation in the furnace opening.

[0099] In addition, if an atmosphere is close to a saturated vapor
pressure or if a flow rate of gas is increased, dew condensation of the
furnace opening tends to increase. However, the heating with the lamp
heater can prevent dew condensation.

[0100] (l) Further, a time period for increasing a temperature of the
furnace opening and the seal cap to a predetermined temperature can be
reduced by heating the furnace opening and the seal cap with the lamp
heater, which improves a manufacturing throughput of semiconductor
devices. For example, as the furnace opening and the seal cap are cooled
when the substrates are loaded into and unloaded from the process
chamber, it is necessary to heat the cooled furnace opening and seal cap
to a predetermined temperature until the process gas is supplied. Since
the lamp heater can heat the furnace opening and the seal cap directly
with radiative heat instead of conductive heat, the furnace opening and
the seal cap can be quickly heated to the predetermined temperature.

[0101] Although the details of the first embodiment has been illustrated
and described, the first embodiment is not limited to the features as set
forth herein, but may be modified in different manners without departing
from the gist of the present disclosure.

[0102] In addition, the inventors of the present disclosure have found,
through careful research, that hydrogen peroxide can be used as a
vaporized precursor gas to improve oxidation efficiency and oxidation
quality of a silicon-containing film. This is described as a second
embodiment below.

Second Embodiment

[0103] Hereinafter, a second embodiment is described.

(1) Configuration of Substrate Processing Apparatus

[0104] First, a configuration of a substrate processing apparatus
according to the present embodiment is described with reference to FIGS.
11 and 12. FIG. 11 schematically illustrates the configuration of the
substrate processing apparatus according to this embodiment, in which a
portion of the processing furnace 202 is shown in a longitudinal
sectional view. FIG. 12 illustrates a longitudinal sectional view of a
hydrogen peroxide vaporization device according to the present
embodiment.

[0105] In the substrate processing apparatus according to the second
embodiment, a hydrogen peroxide supply unit is provided as the gas supply
unit of the substrate processing apparatus according to the first
embodiment. Other configurations have the same structures, and thus,
explanations for such configurations are omitted.

(Gas Supply Unit)

[0106] As shown in FIG. 11, the hydrogen peroxide vapor generator 307 is
connected to the gas supply pipe 233. The hydrogen peroxide vapor
generator 307 is connected with a hydrogen peroxide water source 240d, a
liquid mass flow controller 241d, and a valve 242d via a hydrogen
peroxide solution supply pipe 232d from an upstream side. A hydrogen
peroxide solution, whose flow rate is adjusted by the liquid mass flow
controller 241d, can be supplied into the hydrogen peroxide vapor
generator 307.

[0107] In addition, similar to the first embodiment, the gas supply pipe
233 is equipped with the inert gas supply pipe 232c, the valve 242c, the
MFC 241c, and the inert gas supply source 240c for supplying an inert
gas.

[0109] Additionally, in the second embodiment, since hydrogen peroxide is
used, portions in the substrate processing apparatus, which are exposed
to the hydrogen peroxide, may be made of material hard to react with
hydrogen peroxide. Examples of the material hard to react with hydrogen
peroxide may include ceramics, such as Al2O3, AlN, SiC, and the
like, and quartz. In addition, metal members may be coated with a
reaction prevention film. For example, alumite (Al2O3) may be
used for an aluminum member, and a chromium oxide film may be used for a
stainless member. Members which are not to be heated may be made of
material such as Teflon®, plastics, or the like, which does not react
with hydrogen peroxide.

(Hydrogen Peroxide Vapor Generator)

[0110] FIG. 12 illustrates a configuration of the hydrogen peroxide vapor
generator 307. The hydrogen peroxide vapor generator 307 uses a dropping
method, which vaporizes a precursor solution by dropping the precursor
solution on a heated member. The hydrogen peroxide vapor generator 307
includes a dropping nozzle 300 serving as a liquid supply part for
supplying a hydrogen peroxide solution, a vaporization container 302
serving as a member to be heated, a vaporization space 301 defined by the
vaporization container 302, a vaporizer heater 303 serving as a heating
part for heating the vaporization container 302, an exhaust port 304 for
exhausting a vaporized precursor solution into the reaction chamber, a
thermocouple 305 for measuring a temperature of the vaporization
container 302, the temperature controller 400 for controlling the
temperature of the vaporizer heater 303 based on the temperature measured
by the thermocouple 305, and the hydrogen peroxide solution supply pipe
232d for supplying a precursor solution to the dropping nozzle 300. The
vaporization container 302 is heated by the vaporizer heater 303 such
that the dropped precursor solution is vaporized upon reaching the
vaporization container. In addition, a heat insulating material 306
capable of heat-insulating the hydrogen peroxide vapor generator 307 from
other units is further installed to improve heating efficiency of the
vaporization container 302 by the vaporizer heater 303. The vaporization
container 302 is made of quartz or silicon carbide in order to prevent a
reaction with the precursor solution. The temperature of the vaporization
container 302 is decreased due to a temperature or vaporization heat of
the dropped precursor solution. Accordingly, to prevent such temperature
decrease, it is effective to use silicon carbide, which has high thermal
conductivity.

(2) Substrate Processing Procedure

[0111] Hereinafter, a substrate processing procedure according to the
second embodiment is described with reference to FIG. 13. The substrate
load step (S10) in the substrate processing procedure according to the
second embodiment, as shown in FIG. 13, has the same configuration as
that of the first embodiment, and thus, explanation for the step is
omitted.

(Pressure and Temperature Adjustment Step (S210))

[0112] An interior of the reaction tube 203 is vacuum-exhausted by at
least one of the vacuum pumps 246a and 246b such that an internal
pressure of the reaction tube 203 reaches a desired pressure (degree of
vacuum). In this operation, the internal pressure of the reaction tube
203 is measured by the pressure sensor and a degree of opening of the APC
valve 242 or opening or closing of the valve 240 is feedback-controlled
based on the measured pressure (i.e., pressure adjustment).

[0113] The wafers 200 accommodated in the reaction tube 203 are heated by
the first heating part 207 such that a temperature of the wafers 200
reaches a desired temperature (e.g., 40 degrees C. to 100 degrees C.). In
this operation, the supply of electric power to the first to fourth
heater units 207a to 207d in the first heating part 207 is
feedback-controlled based on temperature information detected by the
first to fourth temperature sensors 263a to 263d such that the
temperature of the wafers 200 in the reaction tube 203 reaches the
desired temperature (i.e., temperature adjustment). Here, the first to
fourth heater units 207a to 207d are controlled to have the same set
temperature.

[0114] While the wafers 200 are heated, the boat rotation mechanism 267 is
actuated to rotate the boat 217. A rotation speed of the boat 217 is
controlled by the controller 121. The boat 217 is maintained to be
rotated until at least a modification step (S220), which will be
described later, is ended.

[0115] Electric power is also supplied to the lamp heater 282, the inlet
tube heater 285, and the exhaust tube heater 284 to adjust a temperature
of the heaters to be in a range from 100 degrees C. to 300 degrees C.
Specifically, the temperature of each of the lamp heater 282, the inlet
tube heater 285, and the exhaust tube heater 284 is adjusted to about 200
degrees C. The three heaters may be controlled to have different
temperatures.

(Modification Step (S220))

[0116] When the wafers 200 are heated and reach the desired temperature
and the boat 217 reaches the desired rotation speed, hydrogen peroxide
water begins to be supplied from the hydrogen peroxide solution supply
pipe (i.e., liquid precursor supply pipe) 232d into the hydrogen peroxide
vapor generator 307. Specifically, the valve 242d is opened, and the
hydrogen peroxide is supplied from the hydrogen peroxide water source
240d into the hydrogen peroxide vapor generator 307 via the liquid mass
flow controller 241d.

[0117] The hydrogen peroxide water supplied into the hydrogen peroxide
vapor generator 307 is dropped from the dropping nozzle 300 onto a bottom
portion of the vaporization container 302. As the vaporization container
302 is heated to a desired temperature (e.g., 150 degrees C. to 170
degrees C.) by the vaporizer heater 303, dropped droplets of the hydrogen
peroxide are instantaneously heated and vaporized to become gas.

[0118] The hydrogen peroxide in a gas state is supplied onto the wafers
200 accommodated in the process chamber 201 via the gas supply pipe 233,
the gas supply nozzle 401, and the gas supply holes 402.

[0119] When the vaporized gas of the hydrogen peroxide water causes an
oxidation reaction with surfaces of the wafers 200, a silicon-containing
film formed on each of the wafers 200 is modified into a SiO film.

[0120] When the hydrogen peroxide water is supplied into the reaction tube
203, the hydrogen peroxide water is exhausted via the vacuum pump 246b
and a liquid collection tank 247. Specifically, the APC valve 255 is
closed and the valve 240 is opened to pass an exhaust gas, which is
exhausted from the reaction tube 203, from the gas exhaust pipe 231
through a separator 244 and a second exhaust pipe 243. Further, after
separating the exhaust gas into a liquid that contains hydrogen peroxide
and a gas that contains no hydrogen peroxide by using the separator 244,
the gas is exhausted from the vacuum pump 246b and the liquid is
collected in the liquid collection tank 247.

[0121] In addition, when the hydrogen peroxide water is supplied into the
reaction tube 203, the valve 240 and the APC valve 255 may be closed to
pressurize the interior of the reaction tube 203. This can make an
atmosphere of the hydrogen peroxide water in the reaction tube 203
uniform.

[0122] After a predetermined period of time elapses, the valve 242d is
closed and the supply of hydrogen peroxide into the reaction tube 203 is
stopped.

[0123] Although the hydrogen peroxide water is described as being supplied
into the hydrogen peroxide vapor generator and the hydrogen peroxide gas
is described as being supplied into the process chamber 201, without
being limited thereto, for example, a liquid that contains ozone
(O3), water (H2O), or the like may be used.

(Purge Step (S230))

[0124] After the modification step (S220) ends, the APC valve 255 is
closed and the valve 240 is opened to vacuum-exhaust the interior of the
reaction tube 203 so that remaining vaporized gas of the hydrogen
peroxide is discharged out of the reaction tube 203. Specifically, as the
valve 242d is closed and the valve 242c is opened, N2 gas (i.e.,
inert gas) as a purge gas is supplied from the inert gas supply pipe 232c
into the reaction tube 203 via the liquid precursor supply nozzle 230
while a flow rate of the purge gas is controlled by the mass flow
controller 241c. Examples of the purge gas may include a rare gas such as
He gas, Ne gas, Ar gas, and the like, in addition to the inert gas such
as the nitrogen (N2) gas. As such, it is possible to purge the
remaining gas to be discharged out of the reaction tube 203. In addition,
when the N2 gas passes through the gas supply nozzle 401, the
hydrogen peroxide gas remaining in the gas supply nozzle 401 can be
extruded and removed. In this operation, the degree of opening of the APC
valve 255 and closing or opening of the valve may be adjusted to exhaust
the remaining hydrogen peroxide from the vacuum pump 246a.

(Temperature Decrease and Return-to-Atmospheric Pressure Step (S240))

[0125] After the purge step (S230) ends, at least one of the valve 240 and
the APC valve 255 is opened to decrease the temperature of the wafers 200
to a predetermined temperature (e.g., room temperature or so) while the
internal pressure of the reaction tube 203 returns to atmospheric
pressure. Specifically, while a valve 242c is opened, N2 gas as an
inert gas is supplied into the reaction tube to increase the internal
pressure of the reaction tube 203 to atmospheric pressure. Electric power
supplied to the first heating part 207 is controlled to decrease the
temperature of the wafers 200.

[0126] While the temperature of the wafers 200 is decreased, the shutters
252, 254, and 256 may be opened, with the blower 257 actuated, to supply
a cooling gas from the cooling gas supply pipe 249 into the space 262
between the reaction tube 203 and the heat insulating member 210 and
exhaust the cooling gas via the cooling gas exhaust pipe 253, while a
flow rate of the cooling gas is controlled by the mass flow controller
251. Examples of the cooling gas may include a rare gas (such as He gas,
Ne gas, and Ar gas), air, or the like, alone or in combination, in
addition to N2 gas. Thus, the space 262 can be rapidly cooled so
that the reaction tube 203 and the first heating part 207 installed in
the space 262 can be cooled in a short time. In addition, the temperature
of the wafers 200 in the reaction tube 203 can be decreased in a shorter
time.

[0127] In addition, the cooling gas such as N2 gas is supplied from
the cooling gas supply pipe 249 into the space 262 such that the space
262 is filled and cooled with the cooling gas while the shutters 254 and
256 are closed, and the shutters 254 and 256 may then be opened, with the
blower 257 actuated, to exhaust the cooling gas in the space 262 via the
cooling gas exhaust pipe 253.

[0128] When the temperature is decreased sufficiently, the supply of the
electric power to the lamp heater 282, the inlet tube heater 285, and the
exhaust tube heater 284 is stopped. The supply of the electric power to
the heaters may be stopped at either the same timing or different
timings.

(Substrate Unload Step (S230))

[0129] The seal cap 219 is then descended by the boat elevator to open the
bottom portion of the reaction tube 203 and, with the processed wafers
200 held on the boat 217, the wafers 200 are unloaded from the bottom
portion of the reaction tube 203 out of the reaction tube 203 (or the
process chamber 201) (i.e., boat unload). Subsequently, the processed
wafers 200 are taken out of the boat 217 (i.e., wafer discharge) and the
substrate processing procedure according to the present embodiment ends.

(3) Effects of the Second Embodiment

[0130] The second embodiment can achieve one or more effects as described
below, in addition to the effects of the first embodiment.

[0131] (a) Since the vaporized gas of the hydrogen peroxide water, which
has higher activation energy and more oxygen atoms in one molecule
(hence, stronger oxidation power) than water vapor (H2O) is used as
the process gas, it can deliver oxygen atoms (O) to a deep portion of a
film formed in a groove of each of the wafers 200 (i.e., a bottom portion
of the groove). Thus, a degree of modification between a surface and a
deep portion of a film on each wafer 200 can be more uniform. As such,
since more uniform substrate processing can be performed between the
surface and the deep portion of the film formed on the wafer 200, a
uniform dielectric constant of the modified wafer 200 can be achieved. In
addition, since the modification step can be performed at a low
temperature in a range from 40 degrees C. to 100 degrees C., performance
of a circuit formed on the wafer 200 can be prevented from being
deteriorated.

[0132] (b) Also, since the hydrogen peroxide has a stronger oxidation
power than water vapor (H2O), processing time can be shortened.

[0133] (c) Additionally, it is possible to prevent the hydrogen peroxide
vapor from being re-liquefied in the reaction tube 203 and around the
inlet tube and the exhaust tube.

[0134] Although the details the second embodiment has been illustrated and
described, the second embodiment is not limited to the features set forth
herein, but may be modified in different manners without departing from
the gist of the present disclosure.

[0135] In addition, the inventors of the present disclosure have found,
through careful research, that vaporizing hydrogen peroxide in the
process chamber 201 can prevent the hydrogen peroxide from being
liquefied. This is described as a third embodiment below.

Third Embodiment

[0136] Hereinafter, a third embodiment will be described below.

(1) Configuration of Substrate Processing Apparatus

[0137] First, a configuration of a substrate processing apparatus
according to the third embodiment will be described with reference to
FIGS. 14 and 15. FIG. 14 schematically illustrates the configuration of
the substrate processing apparatus according to the third embodiment, in
which a portion of the processing furnace 202 is shown in a longitudinal
sectional view. FIG. 15 schematically illustrates a longitudinal
sectional view of the processing furnace 202 in the substrate processing
apparatus according to the third embodiment.

(Gas Supply Unit)

[0138] As shown in FIG. 14, a liquid precursor supply nozzle 501 is
installed between the reaction tube 203 and the first heating part 207.
The liquid precursor supply nozzle 501 is made of, for example, quartz
having low thermal conductivity. The liquid precursor supply nozzle 501
may have a dual-tube structure. The liquid precursor supply nozzle 501 is
disposed along an outer wall of the reaction tube 203. An upper end
portion (i.e., downstream end portion) of the liquid precursor supply
nozzle 501 is air-tightly installed at the top portion (i.e., upper end
opening) of the reaction tube 203. A plurality of supply holes 502 is
formed in the liquid precursor supply nozzle 501 located in the upper end
opening of the reaction tube 203 from an upstream side to an downstream
side (see FIG. 15). The supply holes 502 are formed to cause a liquid
precursor, which is to be supplied into the reaction tube 203, to be
jetted toward the ceiling plate 217c of the boat 217 accommodated in the
reaction tube 203.

[0139] A downstream end portion of a liquid precursor supply pipe 289a for
supplying the liquid precursor is connected to an upstream end portion of
the liquid precursor supply nozzle 501. A liquid precursor supply tank
293, a liquid mass flow controller (LMFC) 294 as a liquid flow rate
controller (i.e., liquid flow rate control unit), an opening/closing
valve 295a, a separator 296, and an opening/closing valve 297 are
sequentially installed in the liquid precursor supply pipe 289a from an
upstream side. In addition, a sub-heater 291a is installed in the liquid
precursor supply pipe 289a, at a more downstream side than at least the
valve 297.

[0140] A downstream end portion of a pumping gas supply pipe 292b for
supplying a pumping gas is connected to a top portion of the liquid
precursor supply tank 293. A pumping gas supply source 298b, a mass flow
controller (MFC) 299b as a flow rate controller (i.e., flow rate control
unit), and an opening/closing valve 295b are sequentially installed in
the pumping gas supply pipe 292b from an upstream side.

[0141] A third heating part 209 is installed in an outer upper portion of
the reaction tube 203. The third heating part 209 is configured to heat
the ceiling plate 217c of the boat 217. An example of the third heating
part 209 may include a lamp heater unit or the like. The controller 121
is electrically connected to the third heating part 209. The controller
121 is configured to control the supply of electric power to the third
heating part 209 at a predetermined timing such that the ceiling plate
217c of the boat 217 reaches a predetermined temperature.

[0142] An inert gas supply pipe 292c is connected between the valve 295a
and the separator 296 of the liquid precursor supply pipe 289a. An inert
gas supply source 298c, a mass flow controller (MFC) 299c serving as a
flow rate controller (i.e., flow rate control unit), and an
opening/closing valve 295c are sequentially installed to the inert gas
supply pipe 292c from an upstream side.

[0143] A downstream end portion of a first gas supply pipe 292d is
connected at a more downstream side than the valve 297 of the liquid
precursor supply pipe 289a. A precursor gas supply source 298d, a mass
flow controller (MFC) 299d serving as a flow rate controller (i.e., flow
rate control unit), and an opening/closing valve 295d are sequentially
installed in the first gas supply pipe 292d from an upstream side. A
sub-heater 291d is installed at a more downstream side than at least the
valve 295d of the first gas supply pipe 292d. A downstream end portion of
a second gas supply pipe 292e is connected at a more downstream side than
the valve 295d of the first gas supply pipe 292d. A precursor gas supply
source 298e, a mass flow controller (MFC) 299e serving as a flow rate
controller (i.e., flow rate control unit), and an opening/closing valve
295e are sequentially installed in the second gas supply pipe 292e from
an upstream side. A sub-heater 291e is installed in the second gas supply
pipe 292e, at a more downstream side than at least the valve 295e.

[0144] Hereinafter, an operation of generating a process gas (or vaporized
gas) by vaporizing a liquid precursor is described. Initially, a pumping
gas is supplied from the pumping gas supply pipe 292b into the liquid
precursor supply tank 293 via the mass flow controller 299b and the valve
295b. Thus, the liquid precursor stored in the liquid precursor supply
tank 293 is supplied into the liquid precursor supply pipe 289a. The
liquid precursor, which has been supplied from the liquid precursor
supply tank 293 into the liquid precursor supply pipe 289a, is supplied
into the reaction tube 203 via the liquid mass flow controller 294, the
valve 295a, the separator 296, the valve 297, and the liquid precursor
supply nozzle 501. The liquid precursor supplied into the reaction tube
203 is then vaporized by contacting with the ceiling plate 217c, which is
heated by the third heating part 209, to generate the process gas (i.e.,
vaporized gas). This process gas is supplied onto the wafers 200 in the
reaction tube 203 and predetermined substrate processing is performed on
the wafers 200.

[0145] In addition, in order to facilitate the vaporization of the liquid
precursor, the liquid precursor flowing into the liquid precursor supply
pipe 289a may be preliminarily heated by the sub-heater 291a. Thus, it is
possible to supply the liquid precursor, which can be easily vaporized,
into the reaction tube 203.

[0146] A liquid precursor supply system mainly includes the liquid
precursor supply pipe 289a, the liquid mass flow controller 294, the
valve 295a, the separator 296, the valve 297, and the liquid precursor
supply nozzle 501. The liquid precursor supply system may include the
liquid precursor supply tank 293, the pumping gas supply pipe 292b, the
pumping gas supply source 298b, the mass flow controller 299b, and the
valve 295b. A gas supply unit mainly includes the liquid precursor supply
system, the third heating part 209, and the ceiling plate 217c.

[0147] An inert gas supply system mainly includes the inert gas supply
pipe 292c, the mass flow controller 299c, and the valve 295c. The inert
gas supply system may include the inert gas supply source 298c, the
liquid precursor supply pipe 289a, the separator 296, the valve 297, and
the liquid precursor supply nozzle 501. A first process gas supply system
mainly includes the first gas supply pipe 292d, the mass flow controller
299d, and the valve 295d. The first process gas supply system may include
the precursor gas supply source 298d, the liquid precursor supply pipe
289a, the liquid precursor supply nozzle 501, the third heating part 209,
and the ceiling plate 217c. A second process gas supply system mainly
includes the second gas supply pipe 292e, the mass flow controller 299e,
and the valve 295e. The second process gas supply system may include the
precursor gas supply source 298e, the liquid precursor supply pipe 289a,
the first gas supply pipe 292d, the liquid precursor supply nozzle 501,
the third heating part 209, and the ceiling plate 217c. Although that the
ceiling plate 217c is described as being installed in the boat 217, the
ceiling plate 217c may be installed in an upper portion of the reaction
tube 203, instead of the boat 217.

[0148] Other configurations are the same as those in the first and second
embodiments and therefore, explanations for such configurations are
omitted.

(2) Substrate Processing Procedure

[0149] Hereinafter, a substrate processing procedure performed as one of
procedures for manufacturing a semiconductor device according to the
present embodiment is described with reference to FIG. 16. Steps except
for a modification step (S320) have the same configurations as those of
the first and second embodiments, and thus, explanations for such steps
are omitted.

(Modification Step (S320))

[0150] When the wafers 200 are heated and reach a desired temperature and
the boat 217 reaches a desired rotation speed, hydrogen peroxide as the
liquid precursor begins to be supplied from the liquid precursor supply
pipe 289a into the reaction tube 203. Specifically, the valves 295c,
295d, and 295e are closed and the valve 295b is opened to supply a
pumping gas from the pumping gas supply source 298b into the liquid
precursor supply tank 293, while a flow rate of the pumping gas is
controlled by the mass flow controller 299b. In addition, the valve 295a
and the valve 297 are opened to supply hydrogen peroxide water stored in
the liquid precursor supply tank 293 from the liquid precursor supply
pipe 289a into the reaction tube 203 via the separator 296 and the liquid
precursor supply nozzle 501, while a flow rate of the hydrogen peroxide
water is controlled by the liquid mass flow controller 294. Examples of
the pumping gas may include inert gases such as nitrogen (N2) gas
and the like, and rare gases such as He gas, Ne gas, Ar gas and the like.

[0151] The hydrogen peroxide water supplied into the reaction tube 203 is
vaporized by contacting with the ceiling plate 217c of the boat 217,
which is heated by the third heating part 209, to generate a vaporized
gas of the hydrogen peroxide water as a process gas. In this manner, the
vaporized gas of the hydrogen peroxide water as the process gas may be
generated in the reaction tube 203. As such, the hydrogen peroxide water
as the liquid precursor has only to be passed through the liquid
precursor supply nozzle 501. The third heating part 209 is preset to a
temperature at which the ceiling plate 217c can be heated to a
temperature (e.g., 150 degrees C. to 170 degrees C.) which vaporize the
hydrogen peroxide water.

[0152] The vaporized gas of the hydrogen peroxide water is supplied onto
the wafers 200 and causes an oxidation reaction with surfaces of the
wafers 200, to modify a silicon-containing film formed on each wafer 200
into a SiO film.

[0153] While the hydrogen peroxide water is supplied into the reaction
tube 203, the hydrogen peroxide water is exhausted via the vacuum pump
246b and the liquid collection tank 247. Specifically, the APC valve 242
is closed and the valve 240 is opened to pass an exhaust gas, which is
exhausted from the reaction tube 203, from the gas exhaust pipe 231
through the separator 244 and the second exhaust pipe 243. Further, after
separating the exhaust gas into a liquid containing hydrogen peroxide and
a gas containing no hydrogen peroxide by means of the separator 244, the
gas is exhausted from the vacuum pump 246b and the liquid is collected in
the liquid collection tank 247.

[0154] In addition, when the hydrogen peroxide water is supplied into the
reaction tube 203, the valve 240 and the APC valve 255 may be closed to
pressurize the interior of the reaction tube 203. This can make an
atmosphere of the hydrogen peroxide water in the reaction tube 203
uniform.

[0155] After a predetermined period of time elapses, the valves 295a,
295b, and 297 are closed the supply of the hydrogen peroxide water into
the reaction tube 203 is stopped.

[0156] The present disclosure is not limited to using the vaporized gas of
the hydrogen peroxide water as the process gas and, for example, a gas
containing a hydrogen element (H) (i.e., hydrogen-containing gas), such
as hydrogen (H2) gas, and a gas containing an oxygen element (O)
(i.e., oxygen-containing gas), such as an oxygen (O2) gas, may be
heated to generate a water vapor (H2O) gas to be used in the present
disclosure. Specifically, the valves 295a, 295b, and 297 may be closed
and the valves 295d and 295e are opened to supply H2 gas and O2
gas from the first gas supply pipe 292d and the second gas supply pipe
292e, respectively, into the reaction tube 203, while flow rates of the
gases are controlled, respectively, by the mass flow controllers 299d and
299e. Water vapor may then be generated as the H2 gas and the
O2 gas supplied into the reaction tube 203 make contact with the
ceiling plate 217c of the boat 217, which is heated by the third heating
part 209, and supplied onto the wafers 200, such that a
silicon-containing film formed on each wafer is modified into a SiO film.
Examples of the oxygen-containing gas may include ozone (O3) gas,
water vapor (H2O), and the like, in addition to O2 gas.

(3) Effects of the Third Embodiment

[0157] The third embodiment can achieve one or more effects as described
below, in addition to the effects of the first and second embodiments.

[0158] (a) Since vaporization occurs in the process chamber 201, no dew
condensation occurs in the gas supply unit, which leads to reducing alien
substances occurring on the wafers 200.

[0159] (b) In addition, since a distance from a gas source to an exhaust
unit is shortened, liquefaction in the exhaust unit can be prevented,
which leads to reducing alien substances on the wafers 200, which may
occur because of a backflow of gas that is re-liquefied or re-vaporized
in the exhaust unit.

[0160] Although the details of the third embodiment has been illustrated
and described, the third embodiment is not limited to the features set
forth herein, but may be modified in different manners without departing
from the gist of the present disclosure.

[0161] In addition, although water (H2O) is described as being used
as a vaporization precursor, gas supplied onto the wafers 200 may include
a state of H2O molecular elements or a state of clusters where
several molecules are combined. In addition, when the gas is generated
from liquid, the gas may be divided to be in a state of H2O
molecular elements or a state of hydrogen (H) atoms and oxygen (O) atoms,
or may be separated to be in a state of clusters where several molecules
are combined. In addition, the gas may be in a state of mist where the
above clusters congregate.

[0162] Similarly, when hydrogen peroxide (H2O2) is used as a
vaporization precursor, gas supplied onto the wafers 200 may also include
a state of H2O molecular elements or a state of clusters where
several molecules are combined. In addition, when the gas is generated
from liquid, the gas may be divided to be in a state of H2O2
molecular elements or a state of clusters where several molecules are
combined. In addition, the gas may be in a state of mist where the above
clusters congregate.

[0163] Further, although the procedure which is a procedure of
manufacturing a semiconductor device, where wafers 200 are processed and,
and also is a procedure of filling a fine groove with an insulator is
described in the above, the present disclosure according to the first to
third embodiments may be applied to procedures other than the
above-described procedure. For example, the present disclosure may be
applied to a procedure of forming an interlayer insulating film of a
semiconductor device substrate, a procedure of sealing a semiconductor
device, and the like.

[0164] Furthermore, although the procedure of manufacturing a
semiconductor device is described in the above, the present disclosure
according to the first to third embodiments may be applied to procedures
other than the above-described procedure. For example, the present
disclosure may be applied to a sealing process for a liquid crystal
substrate in a liquid crystal device manufacturing procedure, a
water-repellent coating process for a glass substrate or a ceramic
substrate used for various kinds of devices, a water-repellent coating
process for mirrors, and the like.

[0165] Additionally, although the process gas is described as water vapor
(H2O), which is generated from oxygen gas and hydrogen gas or is
generated by heating and vaporizing water (H2O) or hydrogen peroxide
(H2O2) water as an oxidant solution, in the above, the present
disclosure is not limited to the above, but may employ a method of
providing mist by applying an ultrasonic wave to water (H2O) or
hydrogen peroxide (H2O2) water, a method of spaying mist by an
atomizer. Further, a method of vaporizing a solution by directly and
instantaneously irradiating the solution with a laser ray or a microwave
may be employed.

[0166] In addition, although the thermal conductor heating part is
described as a lamp heater in the above, the heating part is not limited
thereto, but may be a radiative heating part that emits a laser ray or a
microwave.

[0167] Also, although an example of processing the wafers 200 on which a
polysilazane film is formed is described in the above, the present
disclosure is not limited thereto, but may be applied to the case of
processing a silicon-containing film formed by a CVD method.

<Aspects of Present Disclosure>

[0168] Hereinafter, the some aspects of the present disclosure are
additionally described.

<Supplementary Note 1>

[0169] According to an aspect of the present disclosure, there is provided
a substrate processing apparatus including a reaction tube in which a
substrate is processed; a gas supply unit configured to supply supplies a
process gas to the substrate in the reaction tube; an exhaust unit
configured to exhaust an interior of the reaction tube; a first heating
unit configured to heat the substrate in the reaction tube; a second
heating unit is installed around a connection portion of the exhaust unit
and the reaction tube; and a control unit configured to control a
temperature of the second heating unit when the process gas is supplied
from the gas supply unit.

<Supplementary Note 2>

[0170] In the substrate processing apparatus of Supplementary Note 1, the
temperature of the second heating unit may be controlled to be maintained
at a liquefaction prevention temperature at which the process gas is not
liquefied.

<Supplementary Note 3>

[0171] In the substrate processing apparatus of Supplementary Note 2, the
liquefaction prevention temperature may be in a range from 50 degrees C.
to 300 degrees C.

<Supplementary Note 4>

[0172] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 3, the process gas may contain hydrogen and oxygen.

<Supplementary Note 5>

[0173] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 4, the process gas may contain water molecules.

<Supplementary Note 6>

[0174] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 5, the second heating unit may be installed around a furnace
opening of the reaction tube.

<Supplementary Note 7>

[0175] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 6, a heat insulator may be installed in the furnace opening of
the reaction tube and the second heating unit may be installed below a
top portion of the heat insulator.

<Supplementary Note 8>

[0176] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 7, the second heating unit may be a radiative heating unit.

<Supplementary Note 9>

[0177] In the substrate processing apparatus of Supplementary Note 1 to 8,
the radiative heating unit may heat an inner wall surface of the furnace
opening.

<Supplementary Note 10>

[0178] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 9, the second heating unit may emit light having a peak
wavelength in a range from 0.7 μm to 250 μm.

<Supplementary Note 11>

[0179] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 10, the second heating unit may emit light having a peak
wavelength in a range from 1.3 μm to 200 μm.

<Supplementary Note 12>

[0180] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 11, the second heating unit may emit light having a peak
wavelength in a range from 2 μm to 20 μm.

<Supplementary Note 13>

[0181] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 12, the second heating unit may emit light having a peak
wavelength in a range from 2 μm to 4.5 μm.

<Supplementary Note 14>

[0182] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 13, the second heating unit may be a lamp heater emitting an
infrared ray.

<Supplementary Note 15>

[0183] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 14, the second heating unit may be installed around a portion
of the reaction tube to which the exhaust unit is connected.

<Supplementary Note 16>

[0184] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 15, the second heating unit may be installed in a divided
manner around a portion of the reaction tube to which the exhaust unit is
connected.

<Supplementary Note 17>

[0185] The substrate processing apparatus of any one of Supplementary
Notes 1 to 16 may further include a thermal conductive member such as
thermal conductive ceramic or nonmetallic material coated with thermal
conductive ceramic in the reaction tube.

<Supplementary Note 18>

[0186] In the substrate processing apparatus of Supplementary Note 17, the
thermal conductive member may be installed on a bottom portion of the
reaction tube.

<Supplementary Note 19>

[0187] In the substrate processing apparatus of Supplementary Note 17 or
18, thermal conductivity of the thermal conductive member may be 5 W/mK.

<Supplementary Note 20>

[0188] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 19, an inlet tube heater may be installed in a gas supply port
of the reaction tube around the second heating unit.

<Supplementary Note 21>

[0189] In the substrate processing apparatus of any one of Supplementary
Notes 1 to 20, an exhaust tube heater may be installed in a gas exhaust
port of the reaction tube around the second heating unit.

<Supplementary Note 22>

[0190] In the substrate processing apparatus of Supplementary Note 20 or
21, the liquefaction prevention temperatures of the second heating unit,
the inlet tube heater, and the exhaust tube heater may be controlled
independently or collectively.

<Supplementary Note 23>

[0191] In the substrate processing apparatus of Supplementary Note 22, the
second heating unit, the inlet tube heater, and the exhaust tube heater
may be turned on at least while the gas supply unit supplies the process
gas.

<Supplementary Note 24>

[0192] According to another aspect of the present disclosure, there is
provided a semiconductor device manufacturing apparatus including a
reaction tube in which a substrate is processed; a gas supply unit
configured to supply a process gas to the substrate in the reaction tube;
an exhaust unit configured to exhaust an interior of the reaction tube; a
first heating unit configured to heat the substrate in the reaction tube;
a second heating unit installed around a connection portion of the
exhaust unit and the reaction tube; and a control unit configured to
control a temperature of the second heating unit when the process gas is
supplied from the gas supply unit.

<Supplementary Note 25>

[0193] According to another aspect of the present disclosure, there is
provided a substrate processing method including loading a substrate into
a reaction tube; heating the substrate by a first heating unit installed
in the reaction tube; exhausting an interior of the reaction tube by an
exhaust unit; and supplying a gas, wherein the act of supplying the gas
includes supplying the process gas to a surface of the substrate; and
controlling a temperature of a second heating unit installed around a
connection portion of the exhaust unit and the reaction tube.

<Supplementary Note 26>

[0194] In the substrate processing method of Supplementary Note 25, the
temperature of the second heating unit may be controlled to be maintained
at a liquefaction prevention temperature at which the process gas is not
liquefied.

<Supplementary Note 27>

[0195] In the substrate processing method of Supplementary Note 25, the
process gas may include one or both of water (H2O) molecules and
hydrogen peroxide (H2O2) molecules.

<Supplementary Note 28>

[0196] According to another aspect of the present disclosure, there is
provided a semiconductor device manufacturing method including loading a
substrate into a reaction tube; heating the substrate by a first heating
unit installed in the reaction tube; exhausting an interior of the
reaction tube by an exhaust unit; and supplying a gas, wherein the act of
supplying the gas includes supplying the process gas to a surface of the
substrate; and controlling the temperature of a second heating unit
installed around a connection portion of the exhaust unit and the
reaction tube.

<Supplementary Note 29>

[0197] According to another aspect of the present disclosure, there is
provided a program that causes a computer to perform a process of heating
a substrate by a first heating unit installed in a reaction tube;
exhausting an interior of the reaction tube by an exhaust unit; and
supplying a gas,

[0198] wherein the act of supplying the gas includes supplying a process
gas to a surface of the substrate; and controlling a temperature of a
second heating unit installed around a connection portion of the exhaust
unit and the reaction tube.

<Supplementary Note 30>

[0199] According to another aspect of the present disclosure, there is
provided a non-transitory computer-readable recording medium storing a
program that causes a computer to perform a process of heating a
substrate by a first heating unit installed in a reaction tube;
exhausting an interior of the reaction tube by an exhaust unit; and
supplying a gas, wherein the act of supplying the gas includes supplying
a process gas to a surface of the substrate; and controlling a
temperature of a second heating unit installed around a connection
portion of the exhaust unit and the reaction tube.

<Supplementary Note 31>

[0200] According to another aspect of the present disclosure, there is
provided a heating unit which is installed at an exhaust port side of a
reaction tube accommodating a substrate, and heats the exhaust port side
at a temperature higher than a temperature of the substrate.

<Supplementary Note 32>

[0201] According to another aspect of the present disclosure, there is
provided a substrate processing apparatus including a reaction tube
configured to accommodate a substrate; a gas supply unit configured to
supply a process gas to the substrate in the reaction tube; an exhaust
unit configured to exhaust an interior of the reaction tube; a first
heating unit configured to heat the substrate; a second heating unit
installed around a connection portion of the exhaust unit and the
reaction tube; and a control unit configured to control a temperature of
the second heating unit to a temperature higher than a temperature of the
first heating unit when the process gas is supplied from the gas supply
unit.

<Supplementary Note 33>

[0202] According to another aspect of the present disclosure, there is
provided a substrate processing apparatus including a process chamber
configured to accommodates a substrate; a gas supply unit configured to
supply a process gas to the substrate; a lid member configured to block
the process chamber; a thermal conductor installed on the lid member; and
a thermal conductor heating unit configured to heat the thermal
conductor.

<Supplementary Note 34>

[0203] The substrate processing apparatus of Supplementary Note 33 may
further include a control unit configured to control the thermal
conductor heating unit such that a temperature of the thermal conductor
heating unit is maintained at a liquefaction prevention temperature at
which the process gas is not liquefied.

<Supplementary Note 35>

[0204] In substrate processing apparatus of Supplementary Note 33, the
thermal conductor heating unit may be installed around a furnace opening
of the process chamber.

<Supplementary Note 36>

[0205] In substrate processing apparatus of Supplementary Note 33, the
thermal conductor heating unit may be installed below a top portion of a
heat insulator installed in a furnace opening of the process container.

<Supplementary Note 37>

[0206] In substrate processing apparatus of Supplementary Note 33, the
thermal conductor heating unit may be a radiative heating unit.

<Supplementary Note 38>

[0207] According to another aspect of the present disclosure, there is
provided a thermal conductor which is installed in a lid member
configured to block a process chamber accommodating a substrate and, is
configured to be heated by a thermal conductor heating unit installed
near the lid member.

[0208] According to the substrate processing apparatus of the present
disclosure, it is possible to improve manufacturing quality and
throughput of semiconductor devices.

[0209] While certain embodiments have been described, these embodiments
have been presented by way of example only, and are not intended to limit
the scope of the disclosures. Indeed, the novel methods and apparatuses
described herein may be embodied in a variety of other forms;
furthermore, various omissions, substitutions and changes in the form of
the embodiments described herein may be made without departing from the
spirit of the disclosures. The accompanying claims and their equivalents
are intended to cover such forms or modifications as would fall within
the scope and spirit of the disclosures.